JP2005082610A - Multiphase liquid detergent composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a multiphase liquid detergent composition having excellent usability and detergency and good preservation stability. <P>SOLUTION: The multiphase liquid detergent composition comprises (a) one or more kinds of nonionic surfactant mixtures having a specific distribution of average number of added mol of ethylene oxide, (b) a specified water-soluble inorganic salt and (c) water in specific ratios, respectively. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a multiphase liquid detergent composition that is easy to use and has a cleaning power equivalent to or better than a powder detergent.

  Liquid detergents are superior to powder detergents in terms of ease of use because they can be applied directly to soiled areas. However, there is also a general method in which the liquid detergent is simply dissolved in washing water without being applied to the dirt, and in this case, the cleaning power of the liquid detergent tends to be inferior to that of the powder detergent. This is because, as in the case of the powder detergent, when a builder component such as an alkali agent or a calcium scavenger is sufficiently blended in the composition, a problem occurs in the stability of the system. From this point of view, development of liquid detergents containing builder has been promoted.

  For example, a liquid detergent that is separated into two layers of a liquid surfactant and a builder aqueous solution adjusted to a concentration that is insoluble or hardly soluble in the surfactant, and is used by mixing evenly by shaking immediately before use. (For example, refer to Patent Documents 1 and 2). However, there is a problem that solubility and cleaning performance are not sufficient.

  Moreover, the aqueous | water-based fluid detergent composition containing the effective amount of detergent builder which can be added by pouring is disclosed (for example, refer patent document 3). However, since the composition achieves storage stability by increasing thixotropy, the viscosity at a low shear rate becomes very high and can be added by pouring. There are problems such as sagging, and the solubility in water is inferior.

  Further, a non-aqueous liquid detergent composition in which a builder is dispersed in a nonionic surfactant is disclosed (see, for example, Patent Documents 4, 5, 6, 7, and 8). However, since the composition has a flash point, there is a problem that care must be taken for storage. There were also problems in usability and stability.

Also disclosed is a liquid detergent composition in which lamellar droplets composed of a surfactant containing a peptized polymer having a specific structure are suspended in an aqueous continuous phase (see, for example, Patent Document 9). Although the viscosity also ranges from 30 to 1750 mPa · s, there is a disadvantage that the cleaning power is inferior, especially since inorganic salt builders such as alkaline agents are low in concentration.
JP-A-8-20799 Japanese National Patent Publication No. 11-502898 JP 58-145794 A JP 54-16514 A JP 56-159297 A JP-A-60-230,000 JP 61-204300 A JP-A-2-240200 Japanese National Patent Publication No. 5-501574 Japanese Examined Patent Publication 62-46494

  An object of the present invention is to provide a multiphase liquid detergent composition having excellent usability and detergency. More specifically, the present invention provides a multi-phase liquid detergent composition that improves the detergency that has been a drawback of conventional liquid detergents without sacrificing storage stability while taking advantage of the ease of use of liquid detergents. It is to be.

The present invention comprises (a) a mixture of one or more nonionic surfactants selected from the following (I) to (III) [hereinafter referred to as component (a)] 1 to 60% by mass, (b) alkali metal sulfuric acid At least one water-soluble inorganic salt selected from a salt, an alkali metal carbonate, and an ammonium or alkylammonium chloride or bromide (hereinafter referred to as component (b)), and (c) water (hereinafter referred to as (c) This component relates to a multiphase liquid detergent composition containing 15 to 85% by mass and having a mass ratio of (b) to (c) of 10/90 to 60/40 in terms of (b) / (c).
<Nonionic surfactant mixture (I)>
A mixture of nonionic surfactants represented by the following general formula (I), wherein the total number of compounds in which n in formula (I) is 2 to 15 is 50% by mass or more R ¹ —O— ( _{CH 2 CH 2 O) n H} (I)
[Wherein, R ¹ represents an alkyl group or alkenyl group having 10 to 18 carbon atoms, and n represents an integer of 1 or more. ]
<Nonionic surfactant mixture (II)>
A mixture of nonionic surfactants represented by the following general formula (II), wherein the total number of compounds wherein m is 2 to 15 in the formula (II) is 50% by mass or more R ² —CO— ( OCH ₂ CH ₂ ) _m -OR ³ (II)
[Wherein, R ² represents an alkyl group or alkenyl group having 10 to 18 carbon atoms, R ³ represents an alkyl group or alkenyl group having 1 to 20 carbon atoms, and m represents an integer of 1 or more. ]
<Nonionic surfactant mixture (III)>
A mixture of nonionic surfactants represented by the following general formula (III), wherein the sum of the compounds wherein p in formula (III) is 2 to 15 is 50% by mass or more R ⁴ —O— ( CH ₂ CH ₂ O) _p (R ⁵ O) _q H (III)
[Wherein, R ⁴ represents an alkyl group or alkenyl group having 10 to 18 carbon atoms, R ⁵ represents an alkylene group having 3 to ⁵ carbon atoms, p represents an integer of 1 or more, and q represents an integer of 1 or more. ]

<(A) component>
The multiphase liquid detergent composition of the present invention contains 1 to 60% by mass of a nonionic surfactant represented by the following general formulas (I) to (III) as the component (a). In terms of cleaning performance, stability, and solubility, 5 to 55% by mass is preferable, 10 to 50% by mass is more preferable, and 15 to 45% by mass is still more preferable. Among these, it is preferable to contain a nonionic surfactant represented by (I) or (II), and it is particularly preferable to contain a nonionic surfactant represented by (I).
R ¹ —O— (CH ₂ CH ₂ O) _n H (I)
[Wherein, R ¹ represents an alkyl group or alkenyl group having 10 to 18 carbon atoms, and n represents an integer of 1 or more. Here, in the nonionic surfactant mixture represented by the formula (I), the total of n is 2 to 15 (preferably 4 to 12, more preferably 6 to 10 in terms of cleaning performance and solubility). Is 50% by mass or more (preferably 60% by mass or more, more preferably 70% by mass or more in terms of cleaning performance and solubility). ]
R ² —CO— (OCH ₂ CH ₂ ) _m —OR ³ (II)
[Wherein, R ² represents an alkyl group or alkenyl group having 10 to 18 carbon atoms, R ³ represents an alkyl group or alkenyl group having 1 to 20 carbon atoms, and m represents an integer of 1 or more. Here, in the nonionic surfactant mixture represented by the formula (II), m is 2 to 15 (preferably 4 to 12, more preferably 6 to 10 in terms of cleaning performance and solubility). Is 50% by mass or more (preferably 60% by mass or more, more preferably 70% by mass or more in terms of cleaning performance and solubility). ]
R ⁴ —O— (CH ₂ CH ₂ O) _p (R ⁵ O) _q H (III)
[Wherein, R ⁴ represents an alkyl group or alkenyl group having 10 to 18 carbon atoms, R ⁵ represents an alkylene group having 3 to ⁵ carbon atoms, p represents an integer of 1 or more, and q represents an integer of 1 or more. Here, in the nonionic surfactant mixture represented by the formula (III), p is 2 to 15 (preferably 4 to 12, more preferably 6 to 10 in terms of cleaning performance and solubility). Is 50% by mass or more (preferably 60% by mass or more, more preferably 70% by mass or more in terms of cleaning performance and solubility). ]

  These nonionic surfactants represented by the general formulas (I) to (III) are all mixtures of compounds represented by the formula. In the present invention, as the component (a), an oxyethylene group A nonionic surfactant mixture in which the proportion of compounds having an average added mole number in a specific range is in a specific range is used.

<(B) component>
The multiphase liquid detergent composition of the present invention comprises, as component (b), at least one water-soluble inorganic substance selected from alkali metal sulfates, alkali metal carbonates, and ammonium or alkylammonium chlorides or bromides. Contains salt. In addition, about (b) component, water solubility means melt | dissolving 10 g / L or more in 25 degreeC ion-exchange water.

  In terms of cleaning performance, stability, and solubility, the content of the component (b) is preferably 5 to 40% by mass, more preferably 5 to 30% by mass, and still more preferably 10 to 25% by mass in the composition. . As an alkali metal, sodium and potassium are preferable in terms of cleaning performance.

  From the viewpoint of stability, the component (b) is preferably dissolved in 98% by mass or more in the multiphase liquid detergent composition at 5 ° C., more preferably 99% by mass or more, and substantially completely dissolved. More preferably.

  From the viewpoint of cleaning performance, it is preferable to contain an alkali metal carbonate or an alkali metal silicate, and more preferably an alkali metal carbonate.

<(C) component>
The multiphase liquid detergent composition of the present invention contains 15 to 85% by mass of water as the component (c). 15-70 mass% is preferable at the point of washing | cleaning performance, stability, and solubility, 20-60 mass% is more preferable, and 30-50 mass% is still more preferable.

  The mass ratio of the component (b) to the component (c) is 10/90 to 60/40 in terms of (b) / (c), and is preferably 15/85 to 50/50 in terms of stability. 80-45 / 55 is more preferable, and 25 / 75-40 / 60 is still more preferable.

<Multiphase liquid detergent composition>
In the present invention, the multiphase refers to a state in which a surfactant is salted out and a plurality of phases are present.

  In the multiphase liquid detergent composition of the present invention, the pH at 20 ° C. according to the method described in JIS K 3362: 1998 is preferably 6 to 12 and more preferably 7 to 11 in terms of cleaning performance and damage. 8-11 are more preferable, 9-11 are especially preferable, and 10-11 are the most preferable.

  Further, the surfactant equivalent of JIS K 3362: 1998 of the multiphase liquid detergent composition of the present invention is preferably 10 to 60% by mass, more preferably 15 to 50% by mass in terms of cleaning performance and solubility. Preferably, 20 to 45 mass% is more preferable, and 20 to 40 mass% is particularly preferable. In particular, it is preferable to combine the component (a) with an anionic surfactant in terms of cleaning performance and solubility.

  The viscosity (B-type viscometer, 60 r / min, 60 seconds, 20 ° C.) during use of the multiphase liquid detergent composition of the present invention is preferably 30 to 2000 mPa · s in terms of stability and usability. 50-1800 mPa · s is more preferable. These viscosities were measured using a B-type viscometer (manufactured by Tokyo Keiki Co., Ltd., VISCOMETER MODEL DVM-B) under the conditions of 3 or 4 rotors, a rotation speed of 60 r / min, and a measurement time of 60 seconds. It has been done.

  The multiphase liquid detergent composition of the present invention may be separated into two layers to be used by shaking and mixing immediately before use, but a stable emulsified form is preferred from the viewpoint of usability. In this case, the volume average particle diameter of the droplets is preferably 20 μm or less from the viewpoint of stability and solubility, and is preferably 0.1 μm or more for obtaining productivity and an appropriate viscosity. More preferably, it is 0.2-15 micrometers, More preferably, it is 0.2-10 micrometers. The volume average particle diameter can generally be controlled by the stirring speed during preparation of the composition.

  When the volume average particle diameter is 10 μm or more, the volume average particle diameter of the droplet can be determined by measuring any 500 points with an optical microscope. Is preferably obtained by measuring an arbitrary 500 points with a cryo SEM.

<(D) component>
The multiphase liquid detergent composition of the present invention preferably further contains 0.1 to 10% by mass of (d) a water-soluble polymer compound in terms of stability. In terms of stability and solubility, 0.2 to 8% by mass is preferable, 0.3 to 7% by mass is more preferable, and 0.5 to 5% by mass is still more preferable.

  Moreover, 2000-8 million is preferable, as for the weight average molecular weight of (d) component, More preferably, it is 2000-7 million, More preferably, it is 3000-6 million, Most preferably, it is 5000-6 million. Here, the weight average molecular weight is measured using gel permeation chromatography (GPC), and the average molecular weight is determined in terms of polyethylene glycol (PEG).

  In addition, regarding the component (d), “water-soluble” means that 1 g / L or more dissolves in ion-exchanged water at 25 ° C.

  The multiphase liquid detergent composition of the present invention has a viscosity (B-type viscometer, 60 r / min, 60 seconds, 20 ° C.) of 0. 0 compared to a composition having a composition obtained by removing the component (d) from the composition. It is preferably 7 to 1.3 times, more preferably 0.8 to 1.2 times, and still more preferably 0.8 to 1.0 times.

  From the viewpoint of stability, the component (d) is preferably dissolved in the multiphase liquid detergent composition.

Examples of the component (d) include a polymer having a function of stably maintaining a state in which droplets (mainly containing a salted-out surfactant) are dispersed in the composition. Any polymer can be used. Examples of the polymer having such a function include a segment (A) having an affinity for an aqueous phase and / or a segment (B) having an affinity for the droplet, wherein the segment (A) and ( (B) a polymer having a mass ratio of (A) / (B) = 30/70 to 90/10 (hereinafter referred to as Type 1), or (A) / (B) = 100/0 to 95/5 (Hereinafter referred to as Type 2), or (b) / (b) = 5/95 to 0/100 (hereinafter referred to as Type 3). Of these, Type 1 and Type 2 polymers are preferred in view of stability and solubility, and Type 1 polymers are particularly preferred.
The segment (a) is preferably a polymer chain, and the segment (b) is preferably a polymer chain or an organic group.

  Although the details of the action mechanism of the above water-soluble polymer are unknown, the Type 1 polymer functions as an emulsifier for droplets, and the Type 2 polymer functions as an aqueous phase thickener by dissolving in the aqueous phase. It is considered that the specific gravity of the polymer is controlled by controlling the specific gravity by dissolving in the droplet.

  In the case of a polymer chain, having affinity means that a polymer having a weight average molecular weight of about 2000 to 50,000 having essentially the same structure as the polymer chain or a monomer having the polymer chain is dissolved or uniformly dispersed in a target phase. Specifically, the polymer or monomer is mixed in the target phase at a concentration of 5% by mass, stirred at 60 ° C. for 30 minutes, returned to room temperature (25 ° C.), and allowed to stand 1 After the time, it can be visually confirmed that the polymer or monomer is dissolved or uniformly dispersed because no precipitate or separated layer is formed. Here, the “target phase” refers to each phase generated when the composition of the present invention is mixed and centrifuged after removing the water-insoluble solid component such as inorganic builder particles and the component (d).

  In the case of an organic group, having affinity means that any monomer having an organic group is dissolved or uniformly dispersed in the target phase. Specifically, the monomer is added in the target phase. After mixing at a concentration of 5% by mass, stirring at 60 ° C. for 30 minutes, returning to room temperature (25 ° C.), and after standing for 1 hour, the monomer is dissolved or homogeneous by visual observation that no precipitation or separation layer occurs. It can be confirmed that they are dispersed.

[Segment (I)]
The segment (a) is preferably a polymer chain having an anionic group or a salt thereof in the structural unit, more preferably a polymer chain having a carboxy group or a salt thereof in the structural unit, a sulfonic acid group, A phosphoric acid group, a phosphonic acid group or a salt thereof may be contained.

  Such a polymer chain is preferably a (co) polymer of a vinyl monomer having a carboxy group or a salt thereof (the (co) polymer refers to a single polymer or a copolymer). Examples of the monomer include (meth) acrylic acid [(meth) acrylic acid means acrylic acid, methacrylic acid or a mixture thereof] and salts thereof, styrene carboxylic acid and salts thereof, maleic acid monomer [maleic anhydride] Acid, maleic acid, maleic acid monoester, maleic acid monoamide or a mixture of two or more thereof] and salts thereof, itaconic acid and salts thereof, and the like, and one or more selected from these can be used.

For the part having a sulfonic acid group or a salt thereof, a (co) polymer of a vinyl monomer having a sulfonic acid group or a salt thereof is preferable. Examples of the monomer include 2- (meth) acryloyloxyethanesulfonic acid, 2- (meth) acryloyloxypropanesulfonic acid, 2- (meth) acrylamido-2-alkyl (1 to 4 carbon atoms) propanesulfonic acid, vinylsulfone. Examples thereof include sulfonic acid monomers such as acid and styrene sulfonic acid, and one or more selected from these can be used.
A vinyl monomer (co) polymer having a phosphoric acid group or a salt thereof is preferred at a site having a phosphoric acid group or a phosphonic acid group or a salt thereof.

  Examples of the monomer include (meth) acryloyloxyalkyl (C1-4) phosphoric acid, vinylphosphonic acid and the like.

  These salts include alkali metal, alkaline earth metal, ammonium, alkyl or alkenyl ammonium having 1 to 22 carbon atoms, alkyl or alkenyl substituted pyridinium having 1 to 22 carbon atoms, alkanol ammonium having 1 to 22 carbon atoms, Or a basic amino acid etc. are mentioned, An alkali metal salt like sodium and potassium is preferable.

[Segment (b)]
Examples of the segment (b) include (b 1) a nonionic polymer chain and (b 2) an organic group.

  Examples of the nonionic polymer chain include those having a structural unit derived from a monomer selected from the following monomer groups (B1-1) to (B1-8), or the following polymers (B1-9) to (B1). -11) is preferred.

(B1-1) Vinyl ethers having an unsubstituted or substituted, saturated or unsaturated alkyl group or aralkyl group having 1 to 22 carbon atoms. For example, methyl vinyl ether, ethyl vinyl ether, 4-hydroxybutyl vinyl ether, phenyl vinyl ether and the like are preferable.

(B1-2) Substituted (meth) acrylamides which are unsubstituted or have a saturated or unsaturated alkyl group or aralkyl group having 1 to 12 carbon atoms on nitrogen. For example, (meth) acrylamide, N-methyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-t-butyl (meth) acrylamide, (meth) acryloylmorpholine, 2 -(N, N-dimethylamino) ethyl (meth) acrylamide, 3- (N, N-dimethylamino) propyl (meth) acrylamide, 2-hydroxyethyl (meth) acrylamide, N-methylol (meth) acrylamide, N- Butoxymethyl (meth) acrylamide and the like are preferable.

(B 1-3) N-vinyl aliphatic amides. For example, N-vinylpyrrolidone, N-vinylacetamide, N-vinylformamide and the like are preferable.

(B 1-4) (meth) acrylic acid esters having an unsubstituted or substituted, saturated or unsaturated alkyl group or aralkyl group having 1 to 22 carbon atoms. For example, methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2- (N, N-dimethylamino) ethyl (meth) acrylate, 2- (meth) acrylic acid 2- Methoxyethyl, polyethylene glycol mono (meth) acrylic acid ester and the like are preferable.

(Ro 1-5) Alkylene oxides. For example, ethylene oxide and propylene oxide are preferable.

(Ro 1-6) Cyclic imino ethers. For example, 2-methyl-2-oxazoline, 2-phenyl-2-oxazoline and the like are preferable.

(B 1-7) Styrenes. For example, styrene, 4-ethylstyrene, α-methylstyrene and the like are preferable.

(B 1-8) Vinyl esters. For example, vinyl acetate and vinyl caproate are preferable.

(Bro 1-9) Polyesters composed of a dihydric alcohol and a divalent carboxylic acid. For example, polyethylene glycol and terephthalic acid, or a polycondensate of 1,4-butanediol and succinic acid is preferable.

(B 1-10) Polyamides. For example, a ring-opening polymer of N-methylvalerolactam is preferable.

(Ro 1-11) Polyurethanes. For example, polyethylene glycol, hexamethylene diisocyanate, and a polyaddition product of N-methyl-diethanolamine or 1,4-butanediol are preferable.

  Among these, a polymer chain having an alkyleneoxy group obtained by polymerizing an alkylene oxide of (ro 1-5) as a structural unit is particularly preferable.

  In the case of a polymer chain having an alkyleneoxy group as a structural unit, in the polymer chain (b), the alkyleneoxy group is preferably an ethyleneoxy group and / or a propyleneoxy group, and the ethyleneoxy group and the propyleneoxy group may each be a homopolymer. It may be a block or random copolymer. The average degree of polymerization of the polymer chain (b) is preferably 40 to 200, and more preferably 80 to 150 from the stability of the liquid detergent composition. The terminal of the alkyleneoxy group is not limited, and may have a hydroxyl group or a hydrocarbon group, and may be an ether bond such as a methoxy group, an ethoxy group, or a phenyl group. The hydrocarbon group is preferably an alkyl group having 1 to 12 carbon atoms. More preferably, it is 1-3 alkyl groups.

(B2) Organic group The organic group is preferably a hydrocarbon group having 8 to 30 carbon atoms, more preferably 12 to 22 carbon atoms, and particularly preferably a linear or branched alkyl group having these carbon numbers. Or an alkenyl group. Such a hydrocarbon group is introduced by a monomer having the hydrocarbon group. Examples of such monomers include the following.

(B2-1) A (meth) acrylic acid ester having a saturated or unsaturated alkyl group or aralkyl group having 8 to 30 carbon atoms, preferably 12 to 22 carbon atoms. For example, decyl (meth) acrylate, lauryl (meth) acrylate, myristyl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, behenyl (meth) acrylate, stearyloxypolyethylene glycol monomethacrylate Acid ester etc. are mentioned.

(B2-2) Substituted (meth) acrylamide having 1 or 2 of a saturated or unsaturated alkyl group or aralkyl group having 8 to 30 carbon atoms, preferably 12 to 22 carbon atoms, bonded to nitrogen. For example, N-lauryl (meth) acrylamide, N-dioctyl (meth) acrylamide, etc. are mentioned.

(B 2-3) Vinyl ether having a saturated or unsaturated alkyl group or aralkyl group having 8 to 30 carbon atoms, preferably 12 to 22 carbon atoms. Examples thereof include lauryl vinyl ether, myristyl vinyl ether, palmityl vinyl ether, stearyl vinyl ether and the like.

  As a type 1 polymer, the segment (b) is a polymer chain having a carboxy group or a salt thereof in the structural unit, and the segment (b) is a nonionic polymer chain or a hydrocarbon group having 8 to 30 carbon atoms. Preferably, the segment (b) is a polymer chain having a carboxy group or a salt thereof in a structural unit, and the segment (b) is a polymer having a polymer chain having an alkyleneoxy group as a structural unit, preferable.

  In the type 1 polymer, the mass ratio of segment (a) to segment (b) is (a) / (b) = 30/70 to 90/10, preferably 35/65 to 85/15, and 40/60 ~ 80/20 is more preferred.

  The water-soluble polymer having the segment (a) and the segment (b) is preferably a block type or graft type polymer, and more preferably a graft type polymer.

  The method for synthesizing the block type or graft type polymer is not particularly limited, and a known method can be selected. Among them, a method for polymerizing vinyl monomers and the like using a macroazo initiator having an azo group in a polymer chain (macroazo initiator method), a polymer, using one or more liquids constituting a liquid detergent composition as a solvent A method using a compound having a polymerizable group at one end of the chain (macromonomer method), a radical polymerization of a monomer in the presence of a polymer, and a newly generated polymer chain coexisting in advance by a chain transfer reaction And a method in which another polymer terminal is reacted with a functional group in the polymer chain to cause grafting.

  Preferred examples of the Type 1 polymer include the following: 6. Is particularly preferred.

1. Copolymer of ester (preferably monoester) of polyalkylene glycol and vinyl monomer having carboxy group or salt thereof, and vinyl monomer having carboxy group or salt thereof Polyalkylene glycol (meth) acrylate ester and carboxy group Alternatively, a copolymer with a vinyl monomer having a salt thereof is more preferable, and a copolymer of a polyalkylene glycol (meth) acrylic acid ester and (meth) acrylic acid or a salt thereof is particularly preferable. For example, a copolymer of polyethylene glycol mono (meth) acrylic acid ester and (meth) acrylic acid or a salt thereof, poly (ethylene glycol / propylene glycol) mono (meth) acrylic acid ester and (meth) acrylic acid or a salt thereof And a copolymer thereof.

2. Copolymer of polyalkylene glycol ether having a reactive unsaturated group (radically polymerizable unsaturated group) and a vinyl monomer having a carboxy group or a salt thereof Polyalkylene glycol ether having a reactive unsaturated group and (meth) A copolymer of acrylic acid or a salt thereof and / or a maleic monomer is preferred. Examples thereof include a copolymer of polyethylene glycol allyl ether and maleic acid (or a salt thereof).

3. Copolymer obtained by grafting a monomer having a carboxy group or a salt thereof onto polyalkylene glycol For example, radical polymerization of acrylic acid and maleic acid or a salt thereof in polyethylene glycol, polypropylene glycol or poly (ethylene glycol / propylene glycol) Preferred is a graft polymer obtained.

4). A (co) polymer of a vinyl monomer having a carboxy group or a salt thereof using a polyalkylene glycol macroazo initiator, preferably a block polymer obtained by radical polymerization of (meth) acrylic acid or a salt thereof.

5. Graft polymer obtained by linking a polymer of a vinyl monomer having a carboxy group or a salt thereof and a polyalkylene glycol having a hydroxyl group at the terminal by a dehydration reaction. Preferably, poly (meth) acrylic acid or a salt thereof and a hydroxyl group at the terminal And a graft polymer obtained by linking polyethylene glycol having a dehydration reaction.

6). Copolymer of a vinyl monomer having a carboxy group or a salt thereof and a vinyl monomer having a hydrocarbon group having 8 to 30 carbon atoms (meth) acrylic acid or a salt thereof and an alkyl group having 8 to 30 carbon atoms (meta ) A copolymer with an acrylic ester is preferred.

  1. ~ 6. In addition, vinyl monomers having a sulfonic acid group as part of segment (a), such as styrene sulfonic acid and / or its salt, 2-acrylamido-2-methylpropane sulfonic acid and / or its salt are more preferred May be replaced with (meth) allylsulfonic acid and / or a salt thereof, etc., and as a part of the segment (b), the above-mentioned (b1-1) to (b1-3), (b1-7), (Bro 1-8) may be substituted. Further, vinyl monomers having a cationic group, preferably 2-((meth) acryloyloxy) ethyltrimethylammonium chloride, vinylbenzyltrimethylammonium chloride, 2-((meth) ethyl sulfate, within a range not impairing the effects of the present invention. Acrylicyloxy) ethyldimethylethylammonium chloride, 3-((meth) acrylamide) propyltrimethylammonium chloride, diallyldimethylammonium chloride and the like may be further copolymerized.

  As the type 2 polymer, the segment (a) is preferably a polymer chain having a carboxy group or a salt thereof, or a sulfonic acid group or a salt thereof in a structural unit, and these are the total amount of the segment (a) in the polymer. It is preferable that the ratio which occupies with respect to is 85-100 mass%, It is more preferable that it is 90-100 mass%, It is especially preferable that it is 95-100 mass%. The mass ratio of the segment (b) and the segment (b) is (b) / (b) = 100/0 to 95/5, but (b) / (b) = 100/0 is preferable.

  The Type 2 polymer is preferably dissolved uniformly in the aqueous phase and not uniformly dissolved in the droplets. Preferred examples of Type 2 polymers include vinyl monomers having carboxy groups or salts thereof and / or (co) polymers of vinyl monomers having sulfonic acid groups or salts thereof, such as acrylic acid and / or salts thereof, methacrylic acid and And / or a salt thereof, styrenesulfonic acid and / or a salt thereof, 2-acrylamido-2-methylpropanesulfonic acid and / or a salt thereof, and a (co) polymer of (meth) allylsulfonic acid and / or a salt thereof. . Further, as a component containing a small amount of the segment (b), the above (b1-1) to (b1-3), (b1-7), and (b1-8) may be further copolymerized. Furthermore, vinyl monomers having a cationic group, preferably 2-((meth) acryloyloxy) ethyltrimethylammonium chloride, vinylbenzyltrimethylammonium chloride, 2-((meth) ethyl sulfate, within a range not impairing the effects of the present invention. Acrylicyloxy) ethyldimethylethylammonium chloride, 3-((meth) acrylamide) propyltrimethylammonium chloride, diallyldimethylammonium chloride and the like may be further copolymerized.

  As the Type 3 polymer, the segment (b) is preferably a polymer having a polymer chain having an alkyleneoxy group as a constituent unit. The proportion of this to the total amount of segments (b) in the polymer is preferably 85 to 100% by mass, more preferably 90 to 100% by mass, and particularly preferably 95 to 100% by mass. preferable. The mass ratio of the segment (b) and the segment (b) is (b) / (b) = 5/95 to 0/100, but (b) / (b) = 0/100 is preferable.

  It is preferable that the Type 3 polymer is uniformly dissolved in the droplets and not uniformly dissolved in the aqueous phase. Preferable examples of Type 3 polymers include polyalkylene glycols such as polyethylene glycol and polypropylene glycol. About this, as a part of segment (b), (b1-1) to (b1-3), (b1-7), (b1-8) may be substituted. Further, vinyl monomers having a sulfonic acid group as a component containing a small amount of segment (a), such as styrene sulfonic acid and / or a salt thereof, 2-acrylamido-2-methylpropane sulfonic acid and / or a salt thereof, more preferably ( A product obtained by further copolymerizing (meth) allylsulfonic acid and / or a salt thereof may be used. Further, vinyl monomers having a cationic group, preferably 2-((meth) acryloyloxy) ethyltrimethylammonium chloride, vinylbenzyltrimethylammonium chloride, 2-((meth) ethyl sulfate, within a range not impairing the effects of the present invention. A copolymer of acryloyloxy) ethyldimethylethylammonium chloride, 3-((meth) acrylamide) propyltrimethylammonium chloride, diallyldimethylammonium chloride, or the like may be used.

<(E) component>
The liquid detergent composition of the present invention contains a chelating agent having a molecular weight of 1000 or less and having a calcium capture amount of 200 to 600 CaCO ₃ mg / g and a calcium stability constant of 2 to 10 as component (e) in terms of cleaning performance. It is preferable, 1-40 mass% is more preferable, 5-30 mass% is still more preferable, and 10-25 mass% is especially preferable.

  Examples of the component (e) include polyphosphate, aluminosilicate, citric acid, diglycolic acid, iminodisuccinic acid, S-aspartic acid-N, N-diacetic acid, serine diacetic acid, nitrilotriacetic acid, and the like. . In view of stability, inorganic chelating agents are preferred. Among these, tripolyphosphate and zeolite are preferable, and zeolite is particularly preferable.

  In the present invention, the calcium stability constant and the calcium capture amount are those obtained by the following method.

(Measurement method of calcium stability constant)
A 0.1 mol / liter NH ₄ Cl—NH ₄ OH (pH 10.0) solution is prepared as a buffer. All sample solutions are prepared using this buffer. For measuring the Ca ²⁺ concentration, an ion meter 920A manufactured by Orion Co., Ltd. and a Ca ²⁺ ion electrode are used. First, a relationship between the calcium chloride concentration and the electrode potential is obtained, and a calibration curve is created. 5.36 La 10 ^-2 mol / l solution of calcium chloride, a 5.36 La 10 ^-4 mol / l solution of a chelating agent sample are prepared. Add 1 ml of calcium chloride solution to 100 ml of chelating agent sample solution and stir for 5 minutes. The remaining Ca ²⁺ concentration is measured using a Ca ²⁺ ion electrode. Assuming that the chelating agent forms a chelate complex with Ca ²⁺ and 1: 1, the calcium stability constant (Ca stability constant) is obtained from the following formula.

(Measurement method of calcium capture amount)
All solutions are prepared using the following buffers. In addition, a calcium ion electrode was appropriately used.
_{Buffer: 0.1M-NH 4 Cl-NH} 4 OH buffer (pH10.0)
(1) Preparation of calibration curve A standard calcium ion solution is prepared, and a calibration curve showing the relationship between the logarithm of the calcium ion concentration and the potential as shown in FIG. 1 is prepared.
(2) Measurement of calcium ion trapping amount
About 0.1 g of sample (chelating agent) is weighed into a 100 ml volumetric flask and diluted with the above buffer solution. To this, a CaCl ₂ aqueous solution (pH 10.0) corresponding to 20000 ppm (calculated in terms of CaCO ₃ ) is dropped from a burette (a blank is also measured).
The dropping is carried out by adding 0.1 to 0.2 ml of an aqueous CaCl ₂ solution, reading the potential at that time, and obtaining the calcium ion concentration from the calibration curve in FIG. The calcium ion concentration at the sample dropping amount A in FIG. 2 is the calcium ion trapping amount of the sample.

<Other ingredients>
The multi-phase liquid detergent composition of the present invention comprises, as optional components, solubilizers such as paratoluenesulfonic acid and benzoate (which also has an effect as a preservative); color transfer inhibitors such as polyvinylpyrrolidone; calcium chloride Enzyme stabilizers such as calcium sulfate, formic acid and boric acid (boron compounds); Fluorescent dyes such as Tinopearl CBS-X (manufactured by Ciba Specialty Chemicals); Silicones for the purpose of imparting flexibility; Silica, silicone; antioxidants such as butylhydroxytoluene and distyrenated cresol; other fluorescent dyes; bluing agents; fragrances; antibacterial preservatives; enzymes;

  In particular, a water-miscible organic solvent can be used from the viewpoint of stability and solubility. A water-miscible organic solvent having a hydroxyl group and / or an ether group is preferred. The content of the water-miscible organic solvent is preferably 0.1 to 30% by mass, more preferably 0.5 to 20% by mass, and still more preferably 1 to 10% by mass in the liquid detergent composition.

  Examples of water-miscible organic solvents include (i) alkanols such as ethanol, 1-propanol, 2-propanol and 1-butanol, (ii) glycols such as propylene glycol, butylene glycol and hexylene glycol, and (iii) diethylene glycol. , Polyethylenes such as triethylene glycol, tetraethylene glycol, polyethylene glycol having an average molecular weight of about 200, polyethylene glycol having an average molecular weight of about 400, dipropylene glycol, tripropylene glycol, polypropylene glycol having an average molecular weight of about 2000, (iv) diethylene glycol Monomethyl ether, diethylene glycol dimethyl ether, triethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol Recall diethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, tripropylene glycol monomethyl ether, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-methylglycerol ether, 2-methylglycerol ether 1,3-dimethylglycerin ether, 1-ethylglycerin ether, 1,3-diethylglycerin ether, triethylglycerin ether, 1-pentylglyceryl ether, 2-pentylglyceryl ether, 1-octylglyceryl ether, 2-ethylhexylglyceryl ether , Alkyl ethers such as diethylene glycol monobutyl ether, (v) 2-phenoxyethanol, diethylene glycol monobutyl Nyl ether, triethylene glycol monophenyl ether, polyethylene glycol monophenyl ether having an average molecular weight of about 480, aromatic ethers such as 2-benzyloxyethanol, diethylene glycol monobenzyl ether, (vi) 2-aminoethanol, N-methylethanolamine N, N-dimethylethanolamine, N, N-diethylethanolamine, diethanolamine, N-methyldiethanolamine, N-butyldiethanolamine, triethanolamine, triisopropanolamine, isopropanolamine mixture (mixture of mono-, di-, and tri) Of the alkanolamines.

  The water-miscible organic solvent is effective as a viscosity modifier and gelation inhibitor of the composition, and includes the above (i) alkanols, (ii) glycols, (iv) alkyl ethers, and (v) aromatic ethers. It is preferable to use two or more selected from the above, more preferably two or more selected from (ii), (iv) and (v), particularly preferably two selected from (ii) and (v) By using the above together, it is possible to effectively achieve viscosity adjustment and gelation suppression of the composition.

  A water-immiscible organic solvent may be used as long as the effect of the water-miscible organic solvent is not impaired. Examples of such organic solvents include paraffins such as octane, decane, dodecane and tridecane, olefins such as decene and dodecene, alkyl halides such as methylene chloride and 1,1,1-trichloroethane, and D-limonene. Examples include terpenes.

  As the surfactant, a nonionic surfactant other than the component (a), an anionic surfactant, a cationic surfactant, and an amphoteric surfactant may be contained. It is preferable to contain an anionic surfactant in terms of cleaning performance and solubility.

Examples of nonionic surfactants other than component (a) include alkyl polysaccharide surfactants represented by general formula (IV), amine oxides represented by general formula (V), fatty acid alkanolamides, polyhydroxy fatty acid amides, and the like. Is mentioned.
R ⁶ − (OR ⁷ ) _x G _y (IV)
[Wherein R ⁶ is a linear or branched alkyl group or alkenyl group having 8 to 18 carbon atoms, or an alkylphenyl group, R ⁷ is an alkylene group having 2 to 4 carbon atoms, and G is a carbon number having 5 or 6 carbon atoms. Residues derived from reducing sugars, x is an average value and is a number from 0 to 6, and y is an average value and is a number from 1 to 10. ]

Wherein, R ⁸ is an average carbon number from 8 to 20, preferably 10 to 18, a residue obtained by removing a hydroxyl group from primary and / or secondary alcohol, or an alkyl group and / or an alkenyl group, or shows a represented by the formula ^{- R 11 C (= O)} NH (CH 2) z. Here, R ¹¹ represents an alkyl group and / or alkenyl group having an average carbon number of 8 to 20, preferably 12 to 18, and z represents an integer of 1 to 5. R ⁹ and R ¹⁰ are the same or different and represent CH ₃ , C ₂ H ₅ or C ₂ H ₄ OH. ]

The following (i) to (d) can be used as the anionic surfactant.
(A) Alkylbenzenesulfonate having an alkyl group having an average carbon number of 10 to 20.
(B) An average of 0.5 to 6 moles of ethylene oxide per molecule having an alkyl group derived from a linear primary alcohol or linear secondary alcohol having an average carbon number of 10 to 20, or an alkyl group derived from a branched alcohol. An alkyl ether sulfate ester salt to which (hereinafter referred to as EO) is added.
(C) Alkyl or alkenyl sulfate ester salts having an average alkyl group or alkenyl group having 10 to 20 carbon atoms.
(D) Fatty acid salts having an average carbon number of 8-20.

  The counter ion of these anionic surfactants is selected from the group consisting of cations such as sodium, potassium, magnesium, calcium and alkanolamine, and mixtures thereof. Monomethyldiethanolamine or dimethylmonoethanolamine may be used. In particular, it is preferable to contain (d) in terms of stability and solubility. The anionic surfactant may be blended in the liquid detergent composition as a neutralized product, or may be neutralized after blending in the liquid detergent composition in the acid form.

  Examples of the cationic surfactant include mono long-chain alkyl or alkenyl quaternary ammonium salts.

  Examples of amphoteric surfactants include alkylcarbobetaines, alkylsulfobetaines, alkylamidohydroxysulfobetaines, alkylamidoamine-type betaines, and alkylimidazoline-type betaines.

Examples 1-5, Comparative Examples 1-2
(1) Manufacture of multiphase liquid detergent composition All components in Table 1 were measured in a 500 cc beaker (inner diameter 90 mm) so that the total amount was 300 g, and homomixer (TK Robotics f) in a 20 ° C water bath. Using a model, TK homomixer MARK II 2.5 type stirring unit, manufactured by Tokushu Kika Co., Ltd.), stirring was performed at 9000 r / min for 10 minutes to prepare a multiphase liquid detergent composition.

(2) Collar stain cleaning power evaluation (preparation of collar red cloth)
A collar lining cloth described in JIS K3362: 1998 is prepared.
(Cleaning conditions and evaluation method)
According to the method for evaluating the cleaning power of a synthetic detergent for clothing described in JIS K 3362: 1998, the cleaning power of the liquid detergent composition shown in Table 1 and the index detergent for determining cleaning power was compared and evaluated according to the following criteria. The results are shown in Table 1. The use concentration of the liquid detergent composition shown in Table 1 was 1.33 g / L. Without making a detergent solution in advance, a collar cloth was put into water used at 5 ° C., then a detergent was put in, and after standing for 1 minute, stirring was started.
◎: Superior to index detergent ○: Equivalent to index detergent ×: Inferior to index detergent

(Note) The components in the table are as follows.
Nonionic surfactant (1): A primary alcohol having 10 to 14 carbon atoms in which EO is added in an average of 10 moles and propylene oxide in an average order of 1 mole in block order, and the added mole of EO is 2 A total of 55% by mass of the non-ionic surfactant (2): an average of 7 moles of EO added to a secondary alcohol having 12 to 14 carbon atoms, and the number of moles of EO added is 2 The total of what is ~ 15 is 55% by mass
-Nonionic surfactant (3): 8 to 10 average EO added to primary alcohol having 10 to 14 carbon atoms, and the total number of EO added moles being 2 to 15 is 55% by mass.
-Nonionic surfactant (4): A carboxylic acid methyl ester having 10 to 14 carbon atoms added with an average of 8 moles of EO, and a total number of EO addition moles of 2 to 15 is 55 masses. %
Nonionic surfactant (5): A primary alcohol having 10 to 14 carbon atoms in which EO is added in an average of 10 moles and PO in an average order of 1 mole in block order, and the added mole of EO is 2 to 15 Is 45% by mass
・ Nonionic surfactant (6): An average of 8 moles of EO added to a methyl ester of a carboxylic acid having 10 to 14 carbon atoms, and the total number of EO added moles of 2 to 15 is 45 mass. %
Anionic surfactant (1): polyoxyethylene alkyl ether sulfate (linear alkyl having 10 to 14 carbon atoms, EO average addition mole number 3, sodium salt)
-Anionic surfactant (2): C10-14 linear alkylbenzene sulfonic acid-Anionic surfactant (3): Fatty acid, LUNAC L-55 (manufactured by Kao Corporation)
・ Zeolite: Toyo Builder (Toyo Soda Co., Ltd.)
-POE monophenyl ether: polyoxyethylene monophenyl ether (EO average 3 mol addition)
Polymer (1): Polyethylene glycol (EO average addition mole number 90) monomethacrylate / methacrylic acid = 50/50 (mass ratio) copolymer (weight average molecular weight 50,000; measured by GPC, converted to polyethylene glycol)
Polymer (2): polyacrylic acid (weight average molecular weight 15,000; measured by GPC, converted to polyethylene glycol)
Polymer (3): polymer compound synthesized by the method of Synthesis Example 1 in paragraph 4 of page 4 of JP-A-10-60476 (weight average molecular weight 10,000; measured by GPC, converted to polyethylene glycol)
-Polymer (4): Polyethylene glycol (weight average molecular weight 10,000)
Enzyme: Everase 16.0L-EX (protease, Novozyme)
・ Fluorescent dye: Chino Pearl CBS-X (manufactured by Ciba Specialty Chemicals)

It is a calibration curve for calculating | requiring a calcium ion concentration from an electric potential.

It is a graph showing a dropping amount of related calcium ion concentration and the CaCl ₂ aqueous solution.

Claims (3)

(A) 1 to 60% by mass of one or more nonionic surfactant mixtures selected from the following (I) to (III), (b) alkali metal sulfate, alkali metal carbonate, and ammonium or alkylammonium At least one water-soluble inorganic salt selected from chlorides or bromides of the above, and (c) 15 to 85% by mass of water, wherein the mass ratio of (b) to (c) is (b) / (c) Multiphase liquid detergent composition which is 10 / 90-60 / 40.
<Nonionic surfactant mixture (I)>
A mixture of nonionic surfactants represented by the following general formula (I), wherein the total number of compounds in which n in formula (I) is 2 to 15 is 50% by mass or more R ¹ —O— ( _{CH 2 CH 2 O) n H} (I)
[Wherein, R ¹ represents an alkyl group or alkenyl group having 10 to 18 carbon atoms, and n represents an integer of 1 or more. ]
<Nonionic surfactant mixture (II)>
A mixture of nonionic surfactants represented by the following general formula (II), wherein the total number of compounds wherein m is 2 to 15 in the formula (II) is 50% by mass or more R ² —CO— ( OCH ₂ CH ₂ ) _m -OR ³ (II)
[Wherein, R ² represents an alkyl group or alkenyl group having 10 to 18 carbon atoms, R ³ represents an alkyl group or alkenyl group having 1 to 20 carbon atoms, and m represents an integer of 1 or more. ]
<Nonionic surfactant mixture (III)>
A mixture of nonionic surfactants represented by the following general formula (III), wherein the sum of the compounds wherein p in formula (III) is 2 to 15 is 50% by mass or more R ⁴ —O— ( CH ₂ CH ₂ O) _p (R ⁵ O) _q H (III)
[Wherein, R ⁴ represents an alkyl group or alkenyl group having 10 to 18 carbon atoms, R ⁵ represents an alkylene group having 3 to ⁵ carbon atoms, p represents an integer of 1 or more, and q represents an integer of 1 or more. ] The multiphase liquid detergent composition according to claim 1, further comprising (d) 0.1 to 10% by mass of a water-soluble polymer compound. The multiphase liquid detergent composition according to any one of claims 1 and 2, further comprising (e) a chelating agent having a molecular weight of 1000 or less and having a calcium capture amount of 200 to 600 CaCO ₃ mg / g and a calcium stability constant of 2 to 10.

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